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Yus, M.; Nájera, C., Science of Synthesis, (2005) 26, 155.
The acidic decomposition of α-diazo ketones [14] can be used for the reduction of primary α-diazo ketones, such as compound 5, to methyl ketones 6 by means of 47% hydriodic acid[1] in chloroform at room temperature[15–17] (Scheme 2). The accepted mechanism for this reaction involves the formation of a diazonium ion, which undergoes nucleophilic substitution with loss of nitrogen to give intermediate α-(iodomethyl) ketones.[14] Hydriodic acid can be replaced by potassium iodide and phosphoric acid, but lower yields are observed.[16] Starting from carboxylic acids, the corresponding diazo ketones are obtained through the reaction of diazomethane with their acyl chlorides.[18] Therefore, this is a mild two-step procedure for converting an acyl chloride into a methyl ketone. Condensation of 1,2-diketones with 4-toluenesulfonyl hydrazine at the less hindered side, followed by elimination of 4-toluenesulfinic acid upon adsorption on basic alumina is an alternative common methodology.[18] Freshly prepared solutions of metallocenes derived from titanium, zirconium, and niobium (prepared by reducing the corresponding metallocene dichlorides with 1 equivalent of magnesium under argon) reduce acyclic α-diazo ketones in very good yields (90–95%).[19]
Meeeee 8 Meeeeeeee ee α-Meeee Meeeeee eeee Meeeeeeee Meee,[88] Meeeeeeeeeeeeeee,[88] eee Meeeeeeeee eeee Meeeeeeeeeeee[88,88]
α-Meeee eeeeeee eee ee eeeeeeeee ee eee eeeeeeeeeeeee α-eeeeeeeeeee eeeeeee ee eeeee- eee eeeeeeeeeeeeee eeeeee- ee eeeeeee-eeeeeeeee M—M eeeeeeeee eee eeee ee eeeeeeeeeeeeeeee ee eee eeeeeeeeeeeee eeeeeee eeeeeeeeeeeee.[88,88] Meeeeeeeeeeeee M—M eeeeeeeee ee eee e eeeeeee eeeeeee, eee ee eeeeeeee ee eee eeee ee eeeeee 8-eeeee-8,8-eeeeee, eeeee eeeeeee eeeeeeeee, eee eeeeeeeeeeeeeeeee eeeeeeeeeeeee, ee eeeeeee ee eee eeeeeeee ee eeeeeee(MM) eeeeeee eeeee eee ee eeeee[88–88] ee eeeeeeeeeee,[88] ee eeee 8-eeeeeeeeeee 8,8-eeeeeeeee. Meeeeeeee eeeeee α-eeeee eeeeeee eeeeeee eeee α-eeeee eeeee ee (M)-8-eeeeeeeeeeeeeee eeee eee eeee eeeeeeeee eeee eeeeeeeeeee ee eeeeeee.[88] Meeeeeeeeee ee eeeeeeee eeee 8,8-eee(eeeee)eeeee-8-eee ee eeeeeee eeee eeeeeee(MM) eeeeeee eeeee ee eeeeeeeee eeeeeeeeeeeeeee eeeeeeeeee 8% ee ee eeeeeee, eeeeeee 8,8-eeeeeeeeeeeee-8-eeee.[88] Meeeeeeeeeeeee eeeeeeeeeeeeeeee eeeee eeeee ee eee eeeeeee(MM)-eeeeeeeee eeeeeeeeeeeee ee α-eeeee eeeeeee ee eee eeeeeeee ee eeeeeee ee eeee eeeeeeeeeeeeeeeeee,[88,88,88] e.e. 8 (Meeeee 8).[88] Meeee 8-eeeeeeeeeeeee eeeeee eeee eeee-8,8-eeeee ee eeeeee e eeeeeeeeeeee eeeee ee e eeeeeeeee ee eeeeeeee.[88] Meeeeeeeeeeeee eeeeeee(MM) eeeeeee eeeeeeeee eeeeeeeeeee ee α-eeeee eeeeeee eeeeeee eeee 8-eeeeeeeeeeeee eeeee eeeeeeee eeeeeee[8.8.8]eeeeeeeeeeeee, eeeee eee eeeeeeeeeee eeeeeeeeeeeee eeee 8,8-eeeeeeeeeeeeeeeee-8(8M)-eee eeee eeeeeeeeeeeeeee eeee.[88] Meeeeeeeeeeeee eeeeee ee eeeeeee-eeeeeeeee M—M eeeeeeeee ee eee γ-eeeeeeee ee ee α-eeeee eeeeee ee e eeeeee eeee eeeeeeee eee eee eeeeeeeee ee eeeeeeeeeeeeeee, eeeeeeee M—M eeee eeeeeeeee ee ee eeeeeeeeeee eeeeee eeee.[88,88] M eeeeee eeeeeee ee eee eeeeeeeee ee e eeeeeeeee ee eee eeeeeeeeee eeeeeeeeee, eeeeeeee ee eeeeeee ee α-eeeee eeeeee ee eeeeeee ee eee eeeeeeee ee eeeeee(MM) eeeeeee.[88] Meeeeeeeeeeeee eeeeeeeeeeeeeeee eeeeeeeee ee eeeeee(MM) ee eeeeeee(MM) eeeee ee e eeeeee eeee eeeeeeeeeee ee eee eeeeeeeee ee eeee eeeeeee eeeeeeee eee eeeee eeeeeeeeeeee eeeeee eeeeeeeee.[88,88]
Meeeeeeeeeeee ee eeee ee eeeeeee eeeeeeeeeee eee eeeeeeeeee eeee eeeee ee eee eeee ee eeeeeeeeeeeeeeeeeeee eee eeeeeeeeeeeeeeeeee[88] eeeeeee eeeeeeeeeee eeee Meeee eeeeeeeeeeeeee.[88] Meeeeeeeeeee-eeeeeeeeee eeeeeeeeee ee 8-eeeeeeeeeeeeeeee-8,8-eeeeee ee eeeeeeee eeeeeeee eeeeeee eeeeeeee eeeeee ee 8-eeeeeeeeeeeeeee-8,8-eeeeee.[88] Mee eeeeeeee eeeeeee ee eeeeeee eeeeeeeeeeeee eeeeee ee e eeeeeee eeeeeeeeeeee ee eee eeeeeeee-eeee eeeeeeee eeeeeeee.
Mee eeeeeeeeee ee eeeeeee[88,88] eee eeeeee[88] α-eeeee eeeeeee eeee eeeeeeeeeeeeeee eeeeeeee eeeee eeee eeeeeeeeee ee eeee α-eeeeeeeee eeeeeee 8[88] (Meeeee 8). Mee eeeeeeee eeeee eeeee ee eeee eeeeeeeeeee ee eeeeeeeeeeeeeee, eeeeeee eeeeeeeeee eeeeeeee eeeeeeeeeeeee eeeeeee e eeeeee ee eeeeee. Meeeeee, β-eeeee-8-eeeeeeeeeee[8.8.8]eeeeee eeeeeeeeeee eeeee eeee eeeeeeeeeeee ee eeee eeeeeeee eeeeeee eeeeeeeeeee eeee M-eeeeeeeeee eeee eeeeeeeee.[88] Meee eee eeeeeeee ee eeeeeeeeeeeeeee eeee eeeeeeeeeeee ee eeeeeeeee ee eee eeeeeeee ee eeeeeeeee eeeee, eeee eeeeeeeeee eee eeeeeeeeeeee eeeee ee eee α-eeeeeeee.[88] Mee α-eeeee eeeeee 8, eeeeeee eeee e-eeeeee, ee eeeeeeeeeee ee eeeeeeee eeee e eeeeeeeeeeeeee eeee eeeeee 88, e eeeeeeeee ee e-eeeee-eeeeeeeeeee[88] (Meeeee 8). Me eee eeee eeeeeeeeee eeee eee eeeeeeeeee ee α-eeeee eeeeeee eeee eeeeeeeeeeee eeeeeeee eeeeeeeee ee β-eee eeeeeee ee eeee eeeeeeeee eeeeeeee ee eeeee eeeeeeeee eeee eeeee ee eeeeee eeee eeeee ee eeeeeeeeee eeee ee eeeeeeee ee eeeee eee eeeeeeeeeeeee α-eeeeeeeee eeeeee.[88,88] Meee eeeeeee eeeeeeeeee eee eeeeeeeeeeee ee ee eeeeee ee e eeeeee. Meeee eeeeeeeee eeeeeeeeee, eeeeeeeeeeee eeee eeeeeeeee eee ee eeeeeeeeeee eeee eeeeeee eeeeeeee ee eeeeeeee eeee eeeeee- ee eeeeeeeeeeee eee eeeeeeeee eeee eeeeeeeeeee ee eeee α,α-eeeeeeeeeee eeeeeee.[88] Meee eeeeeeeee eeeee eeeeeeee eeee eee Meeeeeeeeee'e eeee [eeeeeeee(eeeeeeeee)eeeeeeee eeeeee] ee eeee Meeeeee eeeee,[88] eeee eeeeeeee eeeeeeeee ee eeee eeeee eeeeeeee,[88] eee eeee eeeeeeee ee eeee 8,8-eeeeeeeee.[88]
Meeeeeeeeeee Meeeeeeee
8,8-Meeeeeeeeeeeeee (8); Meeeeee Meeeeeeee:[88]
8,8-Mee(eeeeeeeeeeeeeeeeeee)eeeeeee (8; 88 e, 88 eeee, eeeeeeee eeee eeeeeeeeeeee eeee) eee eeeee eeeeee 8 e ee e eeeeeeeeee eeeeeee eeeeeee ee MMMe8 (888 eM) eee 88% MM (88 eM). Meeee eeeeeeee eee ee eeeeeeeeee 88 eee, M8M (888 eM) eee eeeee. Mee MMMe8 eeeee, eeeeeeee eeee e MMMe8 eeeeeee ee eee eeeeeee eeeeee, eee eeeeee eeeeeeeeeeee eeee M8M, 88% Me8M8M8, M8M, eee. MeMMM8, eee MMe, eee eeeee. Meeee eeeeeeeeeee ee eee eeeeeee, eee eeeee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee [eeeeeee eeeeeeeeeee ee MeMMe, eeeeeeeee eeeee/eeeeeee (MMMMMMM: eeeeeeeeee) 8:8], eee eeeeeee eeeeeeeeeeeeeeeee (eeeeeeeee eeeee) eeee 8; eeeee: 8.88 e (88%); ee 888°M.
8-Meeeeeeeee-8-eee (8); Meeeeee Meeeeeeee:[88]
Me e 888-eM, eeeee-eeeeee eeeee eeeeee eeee e eeeeeeee eeeeee, e eeeeeeeeeee, e eeeeee eeeeeeeee eeeeeeeee ee ee eeeeeeee, eee e eeeeeeee eeeeeeee eee, eee eeeeee MMe8 (8.88 eM, 88 eeee), MMM (88 eM), eee M8M (8.8 eM, 888 eeee). Me eeee eeeeeee eeeeeee eee eeeee (eeee 8 e) e eeee ee 8-eeeeeeeeee-8-eee (8.88 e, 88.8 eeee) ee MMM (88 eM) ee 88°M. Meeee eeeeeeee eee ee eeeeeeeeee eeee ee eee eeee eeeeeeeeeee, M8 eeeeeeeee eee eeeeeeeeeeee. Mee eeeeeeeee eeeeeee eee eeeeeee eeee e 8 M MeMMe eeee eee eeee 88% M8M8 (88 eM), eeeeeeeeeee eee eeeeeeeeeee eeeee 88°M. Mee eeeeeee eeeee eee eeeeee eeee M8M eee eeeeeeeee eeee Me8M (8 × 88 eM). Mee eeeeeeee eeeeeeee eeee eeeee (Me8MM8) eee eeeeeeeeee. Mee eeeeeeeee eee eee eeeeeeeee ee eeeeee 8; eeeee: 8.88 e (88%); ee 88.8–88°M/8.88 Meee.
References
[1] | Meeeee, M. M.; Meeee, M. M., Me Meeeeeeeeeee ee Meeeeeee eee Meeeeee Meeeeeeee, Meeeeeee, M. M., Me.; Meeee: Meeeeeeeee, MM, (8888); Mee. 8, e 8888. |
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Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 88M/8, 888.
- 8.Meeeee-Meee, (8888) 8/8e, 888.